US4169910A - Multilayer film including polyolefin layers and a polybutylene layer useful for the production of bags - Google Patents
Multilayer film including polyolefin layers and a polybutylene layer useful for the production of bags Download PDFInfo
- Publication number
- US4169910A US4169910A US05/919,852 US91985278A US4169910A US 4169910 A US4169910 A US 4169910A US 91985278 A US91985278 A US 91985278A US 4169910 A US4169910 A US 4169910A
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- US
- United States
- Prior art keywords
- film
- multilayer film
- copolymer
- melt flow
- per minute
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- -1 polybutylene Polymers 0.000 title claims abstract description 46
- 229920001748 polybutylene Polymers 0.000 title claims abstract description 21
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000010410 layer Substances 0.000 claims abstract description 36
- 239000012792 core layer Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 229920001519 homopolymer Polymers 0.000 claims abstract description 18
- 229920005606 polypropylene copolymer Polymers 0.000 claims abstract description 10
- 229920005629 polypropylene homopolymer Polymers 0.000 claims abstract description 10
- 239000010813 municipal solid waste Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 27
- 239000000155 melt Substances 0.000 claims description 18
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 6
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 claims description 4
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 3
- QLZJUIZVJLSNDD-UHFFFAOYSA-N 2-(2-methylidenebutanoyloxy)ethyl 2-methylidenebutanoate Chemical compound CCC(=C)C(=O)OCCOC(=O)C(=C)CC QLZJUIZVJLSNDD-UHFFFAOYSA-N 0.000 claims 2
- 239000005042 ethylene-ethyl acrylate Substances 0.000 claims 2
- 238000007789 sealing Methods 0.000 claims 1
- 239000010408 film Substances 0.000 description 93
- 229920000642 polymer Polymers 0.000 description 31
- 230000000704 physical effect Effects 0.000 description 28
- 239000004743 Polypropylene Substances 0.000 description 18
- 229920001155 polypropylene Polymers 0.000 description 15
- 239000002356 single layer Substances 0.000 description 7
- 239000002985 plastic film Substances 0.000 description 5
- 229920006255 plastic film Polymers 0.000 description 5
- HLWRUJAIJJEZDL-UHFFFAOYSA-M sodium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [Na+].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC([O-])=O HLWRUJAIJJEZDL-UHFFFAOYSA-M 0.000 description 4
- 230000032798 delamination Effects 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 240000007930 Oxalis acetosella Species 0.000 description 1
- 235000008098 Oxalis acetosella Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- CGPRUXZTHGTMKW-UHFFFAOYSA-N ethene;ethyl prop-2-enoate Chemical class C=C.CCOC(=O)C=C CGPRUXZTHGTMKW-UHFFFAOYSA-N 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012793 heat-sealing layer Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
- B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/31—Heat sealable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/72—Density
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
- B32B2309/08—Dimensions, e.g. volume
- B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
- B32B2309/105—Thickness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2323/00—Polyalkenes
- B32B2323/04—Polyethylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2323/00—Polyalkenes
- B32B2323/10—Polypropylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2331/00—Polyvinylesters
- B32B2331/04—Polymers of vinyl acetate, e.g. PVA
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2333/00—Polymers of unsaturated acids or derivatives thereof
- B32B2333/04—Polymers of esters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/02—Open containers
- B32B2439/06—Bags, sacks, sachets
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
- Y10T156/1052—Methods of surface bonding and/or assembly therefor with cutting, punching, tearing or severing
- Y10T156/1054—Methods of surface bonding and/or assembly therefor with cutting, punching, tearing or severing and simultaneously bonding [e.g., cut-seaming]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31913—Monoolefin polymer
Definitions
- the present invention relates to a multilayer film, and more particularly to a multilayer plastic film suitable for use in fabricating a trash bag.
- a plastic film suitable for use in fabricating a trash bag must exhibit strong physical properties in order to resist internal and external stresses on the bag. Such a bag could also be suitable for use as a container for shipping goods. In addition to resisting stresses, it is highly advantageous if the plastic film is easily heat sealable in order to simplify the manufacturing operations for producing the bags.
- the heat sealed seams must be strong and be capable of resisting stresses tending to break the seams.
- the instant invention overcomes the prior art problems and provides a film which can be produced economically at relatively high speeds and can be heat sealed to define strong reliable bags.
- a multilayer film suitable for use in fabricating a trash bag including a first outer layer comprising a first heat sealable polyolefin, a second outer layer comprising a second heat sealable polyolefin, and a core layer comprising a blend of a polybutylene homopolymer, and a polypropylene homopolymer or copolymer.
- the invention further comprises a bag fabricated from the multilayer film.
- the present invention also relates to a method of producing the aforementioned multilayer film, comprising the step of coextruding said layers through a single die gap.
- a single layer film of the blend or a two layer thin film having a one layer of the blend is unacceptable.
- the thickness is not uniform and many holes in the film are formed. The appearance of a hole interferes with the formation of a "bubble" in carrying out the blown film extrusion.
- the suitable heat sealable polyolefins include copolymers of ethylene vinyl acetate and ethylene ethyl acrylates each having comonomer contents of from about 1% to 30% by weight and a melt flow of from about 0.3 to about 10.0 decigrams per minute.
- Suitable polyolefins further include polyethylene having a density of from about 0.916 to about 0.962 grams per cubic centimeter and having a melt flow of from about 0.1 to about 10 decigrams per minute.
- the ethylene vinyl acetate copolymer and ethylene ethyl acrylate copolymer each has a comonomer content of from about 1% to about 20% by weight and a melt flow of from about 0.3 to about 5 decigrams per minute.
- the polyethylene has a density of from about 0.916 to about 0.930 gram per cubic centimeter and a melt flow of from about 0.1 to about 6 decigrams per minute.
- polypropylene polymer having a density of from about 0.89 to about 0.91 gram per cubic centimeter and having a melt flow of from about 0.5 to about 15 decigrams per minute is preferable.
- the polybutylene homopolymer has a density of from about 0.90 to about 0.92 gram per cubic centimeter and a melt flow of from about 0.4 to about 10 decigrams per minute.
- all of the polymers used in the invention are film grade.
- the overall thickness of the film of the invention can be from about 0.5 to about 10 mils. Preferably, the overall thickness is from about 1 to about 3 mils.
- the core layer is from about 10% to about 90% of the overall thickness. Most of the strength of the film is derived from the core layer.
- the blend of the polybutylene homopolymer and the polypropylene polymer is in equal amounts.
- the blend can range from about 10% to about 90% by weight of one polymer with the balance being the other, preferably 2:1 to 1:2.
- various conventional additives such as slip agents, antiblocking agents, and pigments can be incorporated in the film of the invention in accordance with the conventional practice.
- Puncture Toughness Generally this test includes driving a 1/2 inch round probe at the rate of 20 inches per minute against a sample of film. The load at puncture is measured along with the area under the load-elongation curve (energy).
- Heat Seal Strength Test Two one-inch wide strips of film are sealed to each other at a central portion and subjected to ASTM D-882 until delamination or a break occurs.
- blowup ratio as used herein is the ratio of the flat width of the blown tube of film to the exit diameter of the die.
- the drawdown ratio as used herein is the ratio of the exterior gap of the die and the thickness of the drawn film.
- Table 1 shows the polymers used in the examples herein.
- Example 1 a multilayer film according to the instant invention was produced in accordance with conventional blown film coextrusion methods using a three layer spiral-channel die having a diameter of 12 inches to form a tube of the film.
- An EGAN die was used.
- the exterior die gap was 30 mils.
- the blowup ratio was about 3:1 and the drawdown ratio was about 20:1.
- Each extruder was supplied with the polymer for forming one of the layers for the film. Each extruder was arranged to feed a separate channel of the three layer die. The multilayer film was extruded through the single die gap. While the multilayer film had only three layers, it is possible to have additional layers by using additional extruders and a multilayer die having a number of channels corresponding to the number of extruders used.
- Each of the outer layers was polymer P-E A and the core layer was an equal blend of polymers P-P A and P-B B.
- the overall thickness of the resulting film was about 1.5 mils and the core layer thickness was about 45% of the total film thickness.
- the inner and outer layers had about the same thickness.
- Example 2 was a monolayer film of polymer P-E A also produced by a similar blown film process and subjected to similar blowup and drawdown ratios.
- Table 2 compares the physical properties of the films of Examples 1 and 2 to each other and includes typical values for a typical prior art film having a thickness of about 1.5 mil.
- Example 1 From Table 2, it is evident that the film of the instant invention, Example 1, possesses superior physical properties with respect to the monolayer film of Example 2 as well as the typical prior art film.
- Examples 3, 4, and 5 were carried out in an endeavor to compare the physical properties of films of the instant invention for different polypropylene polymers. Films were produced for the Examples 3, 4, and 5 in accordance with the process of Example 1 and with the same outer layers and the same ratio for the blend except that an Egan die having a diameter of 8 inches and an exterior gap of 35 mils was used. The polypropylene polymer for each of the examples 3, 4, and 5 is shown in Table 3 along with the measured physical properties. Each of the films for the Examples 3, 4 and 5 had an overall thickness of about 1.5 mil and the thickness of each layer was about equal to each other. For each film, the blowup ratio was about 4:1 and the drawdown ratio was about 35:1.5.
- Example 3 From Table 3, it can be seen that the film of Example 3 had the best physical properties. From Table 1, it can be seen that polymer P-P A has a lower melt flow as compared to polymers P-P B and P-P C and is preferable.
- Examples 6 and 7 were carried out in order to compare the physical properties of films for different core layer thicknesses.
- the films for the Examples 6 and 7 were produced in accordance with the process used for producing the films of the Examples 3 to 5 and each of these films included layers having the same polymer as in the film of the Example 1.
- Table 4 shows a comparison between the films of the Examples 6 and 7.
- Table 4 shows that the core layer provides improved physical properties for an increased thickness.
- Examples 8 and 9 were carried out in order to compare films having different amounts of polypropylene polymer in the core layer.
- the films for the Examples 8 and 9 were produced in accordance with the process used for the films of the Examples 3 to 5.
- Examples 10 and 11 were carried out in order to compare the physical properties of two films which have the same first outer layers and core layers and different second outer layers.
- two films were made in accordance with the process of the Examples 3 to 5 with each film having a thickness of about 3.0 mils instead of 1.5 mil and having layer thickness in the ratio of 1:2:3.
- the first outer layer was polymer P-E A and the core layer was an equal blend of the polymer P-P B and P-B A.
- the second outer layer was polymer P-E A and for the Example 11, the second outer layer was an equal blend of the polymers P-E A and EVA A.
- Table 6 shows a comparison between the measured physical properties of the films of the Examples 10 and 11. This shows the superiority of the blend used in Example 11 as a heat sealing layer.
- Examples 12, 13, 14 and 15 were carried out in order to compare the physical property of films having different blends for the core layers.
- a film having a thickness of 3.0 mils and a ratio of layers of 1:2:3 was produced in accordance with the process of the Examples 3 to 5.
- the outer layers of each of the films were the polymer P-E A and the core layers were a blend of P-P B and P-B A with the ratio of P-P B:P-B A as shown in Table 7.
- the film of the Example 12 tended to delaminate during the heat seal strength test so that a core of 100% polybutylene is unacceptable.
- the film of the Example 13 performed better that the film of the Example 12 during the Heat Seal Strength Test and the films of the Examples 14 and 15 showed some delamination during the Heat Seal Strength Test. Previous tests for comparable films having a thickness of about 1.5 mils showed no delamination.
- Examples 16, 17 and 18 were carried out to further compare films having core layers with different blends.
- Each film having a thickness of 1.5 mil and a ratio of layers of 1:1:1 was produced in accordance with the process of the Examples 3 to 5.
- the outer layers for the films were polymer P-P B while the core layers were blends of polymers P-P B and P-B A with the ratio of P-P B:P-B A as shown in Table 8.
- Examples 19 and 20 were carried out in order to compare the physical properties of two films having core layers with different polybutylene homopolymers.
- the films for the Examples 19 and 20 were made in accordance with the process of the film of the Example 15.
- the film for the Example 19 was similar to the film of the Example 15 and the film for the Example 20 used P-B B for the core layer.
- the physical properties for the Examples 19 and 20 are shown in Table 9. Each film had a thickness of about 3.0 mils.
- the film of the Example 19 exhibits somewhat better physical properties than the film of the Example 20 so that it shows that the lower value of melt flow for the polybutylene is preferable.
- Examples 21, 22, and 23 were carried out in order to compare the physical properties of films having different layer ratios.
- Films for the Examples 21, 22, and 23 were made with outer layers of polymer P-E A and core layers of a blend of equal amounts of polymers P-P B and P-B B. The same process as described for the Examples 3 to 5 was used, but the ratio of the layers for the respective films was as shown in Table 10.
- the film thickness for each example was about 1.5 mils.
- the Example 21 had the greatest core thickness and also had the best physical properties.
- Examples 24 and 25 were carried out in order to measure the physical properties of two films made in accordance with the Example 19 but with the blowup ratios as shown in Table 10. Each film had a thickness of 3.0 mils.
- the film of the Example 25 with the higher blowup ratio exhibited somewhat better physical properties and is preferable.
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Wrappers (AREA)
- Materials For Medical Uses (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
Table 1 ______________________________________ Commercial Melt Flow Identification Polymer dg/min. Description and Source ______________________________________ P-E A 2.0 Polyethylene DYNH-9 Union density: Carbide Corporation 0.919 g/cc P-E B 0.1 Polyethylene density: 0.917 g/cc P-E C 0.3 Polyethylene DGDA 6093 Union density: Carbide Corp. 0.953 g/cc P-P A 0.6 Polypropylene Shell 5220, Shell Homopolymer Chemical Company density: 0.905 g/cc P-P B 3.0 Polypropylene Rexene PP 44J3, Copolymer Rexene Polymers Co. density: 0.900 g/cc P-P C 4.0 Polypropylene Hercules Profax 8531, Copolymer Hercules Chem Co. density: 0.900 g/cc P-P D 7.0 Polypropylene Rexene PP 4451, Homopolymer Rexene Polymers Co. density: 0.905 g/cc P-P E 12.0 Polypropylene PP 9818, Diamond Copolymer Shamrock Chem. Co. density: .899 g/cc P-B A 1.0 Polybutylene Shell 1600, Shell Homopolymer Chemical Co. density: 0.910 g/cc P-B B 2.1 Polybutylene Shell 1200, Shell density: Chemical Co. 0.910 g/cc EVA A 1.0 Ethylene DQDA-1824, Union Vinyl Acetate Carbide Corp. 4% vinyl acetate ______________________________________
Table 2 ______________________________________ (Invention) (Monolayer) Typical Prior Physical Property Example 1 Example 2 Art Film ______________________________________ Puncture Toughness 9.1 5.5 6.3 load (lbs.) Puncture Toughness 20.0 4.5 4.8 energy (inch-lbs.) Tensile Strength, MD 5700 2400 3100 (lbs./in.sup.2) TD 4700 2200 1800 Tensile Energy MD 46 21 20 (in.-lbs.) TD 40 29 27 Dart Drop (g.) 132 85 90 ______________________________________
Table 3 ______________________________________ Physical Properties Example 3 Example 4 Example 5 ______________________________________ Polypropylene polymer in core layer P-P A P-P B P-P C Puncture Toughness 9.7 4.9 4.7 load (lbs.) Puncture Toughness 13.3 5.2 4.8 energy (in.-lbs.) Tensile Strength MD 4000 4100 3700 (lbs./in..sup.2) TD 3800 3000 3200 ______________________________________
Table 4 ______________________________________ Physical Properties Example 6 Example 7 ______________________________________ Core thickness as % of overall thickness 45% 33% Puncture Toughness 9.0 9.7 load (lbs.) Puncture Toughness 20.0 13.3 energy (in./lbs.) Tensile Strength (lbs./in..sup.2) MD 5700 4000 TD 4700 3800 ______________________________________
Table 5 ______________________________________ Physical Properties Example 8 Example 9 ______________________________________ % of P-P A in 50% 67% core layer Puncture Toughness load (lbs.) 9.7 6.0 Puncture Toughness energy (in.-lbs.) 13.3 6.6 Dart Drop (g.) 132 52 ______________________________________
Table 6 ______________________________________ Physical Properties Example 10 Example 11 ______________________________________ Dart Drop (g.) 315 241 Puncture Toughness 10.0 9.6 load (lbs.) Puncture Toughness 12.2 9.8 energy (in.-lbs.) Elmendorf Tear (g.) MD 1046 639 TD 1024 1386 Tensile strength (lbs./in..sup.2) 3300 3900 TD 3600 4000 Heat Seal Strength Test (lbs.) 3.5 5.6 ______________________________________
Table 7 ______________________________________ Physical Example Example Example Example Properties 12 13 14 15 ______________________________________ P-P B:P-B A 0:100 20:80 35:65 50:50 Dart Drop (g.) 346 272 230 315 Puncture Toughness 11.1 8.6 9.1 10.0 load (lbs.) Puncture Toughness 11.4 10.8 9.8 12.2 energy (in.-lbs.) Elmendorf Tear (g.) MD 1202 623 526 1046 TD 1540 1101 1093 1027 Tensile Strength (lbs./in..sup.2) MD 3200 3400 3400 3300 TD 2600 2900 3200 3600 Heat Seal Strength 2.9 4.5 (lbs.) ______________________________________
Table 8 ______________________________________ Physical Properties Example 16 Example 17 Example 18 ______________________________________ P-P B:P-B A 50:50 67:33 100:0 Dart Drop (g.) 84 90 less than 50 Puncture Toughness 5.3 5.2 -- load (lbs.) Puncture Toughness 4.6 3.8 -- energy (in.-lbs.) Elmendorf Tear (g.) MD 330 370 less than 20 TD 1090 880 -- Tensile strength (lbs./in..sup.2) MD 4070 4300 -- TD 3100 3000 ______________________________________
Table 9 ______________________________________ Physical Properties Example 19 Example 20 ______________________________________ Polybutylene Homopolymer P-B A P-B B Dart Drop (g.) 315 211 Puncture Toughness 10.0 10.5 load (lbs.) Puncture Toughness energy 12.2 12.4 (in.-lbs.) Elmendorf Tear (g.) MD 1046 763 TD 1027 1015 Tensile Strength (lbs./in.sup.2) 3300 3300 TD 3600 3400 ______________________________________
Table 10 ______________________________________ Physical Properties Example 21 Example 22 Example 23 ______________________________________ Ratio of layers 1:1:1 2:1:2 3:1:3 Dart Drop (g.) 88 84 88 Puncture Toughness 5.3 5.2 5.2 load (lbs.) Puncture Toughness 4.6 3.8 4.0 energy (in.-lbs.) Elmendorf Tear (g.) MD 330 220 210 TD 1090 890 910 Tensile Strength (lbs./in..sup.2) MD 4070 3800 3500 TD 3100 2800 2800 ______________________________________
Table 10 ______________________________________ Physical Properties Example 24 Example 25 ______________________________________ Blow Up Ratio 3.0 4.0 Dart Drop (g.) 211 214 Puncture Toughness 10.1 10.5 load (lbs.) Puncture Toughness 12.1 12.4 energy (in.-lbs.) Elmendorf Tear (g.) MD 615 763 TD 1316 1015 Tensile Strength (lbs./in..sup.2) 3200 3300 TD 3000 3400 ______________________________________
Claims (30)
Priority Applications (19)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/919,852 US4169910A (en) | 1978-06-28 | 1978-06-28 | Multilayer film including polyolefin layers and a polybutylene layer useful for the production of bags |
CA000328571A CA1156812A (en) | 1978-06-28 | 1979-05-29 | Multilayer film |
DE19792921745 DE2921745A1 (en) | 1978-06-28 | 1979-05-29 | MULTI-LAYER FILM |
SE7904789A SE7904789L (en) | 1978-06-28 | 1979-05-31 | MULTI-LAYER FILM AND SET FOR ITS PRODUCTION |
NO791822A NO791822L (en) | 1978-06-28 | 1979-05-31 | Multilayer films. |
DK231679A DK231679A (en) | 1978-06-28 | 1979-06-01 | MULTI-LAYER FOIL PROCEDURE FOR PREPARATION AND BAG PREPARED THEREOF |
IT4929479A IT1117797B (en) | 1978-06-28 | 1979-06-04 | IMPROVEMENT IN MULTI-LAYER PLASTIC FILMS FOR THE PRODUCTION OF BAG CONTAINERS AND MANUFACTURING PROCEDURE |
BE0/195573A BE876774A (en) | 1978-06-28 | 1979-06-05 | MULTI-LAYER FILM, BAG IMPLEMENTING SUCH FILM AND METHOD FOR MANUFACTURING THE LATTER |
NL7904396A NL7904396A (en) | 1978-06-28 | 1979-06-05 | MULTI-LAYER FOIL AND METHOD FOR MANUFACTURING THE SAME |
JP7050779A JPS555891A (en) | 1978-06-28 | 1979-06-05 | Multilayer film |
GB7919525A GB2025847B (en) | 1978-06-28 | 1979-06-05 | Multilayer film |
AT403479A ATA403479A (en) | 1978-06-28 | 1979-06-05 | MULTILAYER FILM AND METHOD FOR THE PRODUCTION THEREOF |
NZ19064179A NZ190641A (en) | 1978-06-28 | 1979-06-05 | Multilayer plastics film comprising a core layer of polybutylene-polypropylene blend |
MX177941A MX151018A (en) | 1978-06-28 | 1979-06-05 | IMPROVED METHOD FOR OBTAINING A MULTIPLE LAYER FILM AND RESULTING PRODUCT |
FR7914292A FR2434034A1 (en) | 1978-06-28 | 1979-06-05 | MULTI-LAYERED FILM, BAG IMPLEMENTING SUCH FILM AND MANUFACTURING METHOD THEREOF |
CH523579A CH640179A5 (en) | 1978-06-28 | 1979-06-05 | MULTI-LAYERED FILM, BAG CONTAINING SUCH A FILM AND METHOD FOR MANUFACTURING THE SAME. |
FI791794A FI69778C (en) | 1978-06-28 | 1979-06-05 | FLERSKIKTSFILM OCH FOERFARANDE FOER FRAMSTAELLNING AV FILMEN |
AU47858/79A AU528974B2 (en) | 1978-06-28 | 1979-06-07 | Multilayer film |
IE1102/79A IE48575B1 (en) | 1978-06-28 | 1979-08-08 | Multilayer film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/919,852 US4169910A (en) | 1978-06-28 | 1978-06-28 | Multilayer film including polyolefin layers and a polybutylene layer useful for the production of bags |
Publications (1)
Publication Number | Publication Date |
---|---|
US4169910A true US4169910A (en) | 1979-10-02 |
Family
ID=25442747
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/919,852 Expired - Lifetime US4169910A (en) | 1978-06-28 | 1978-06-28 | Multilayer film including polyolefin layers and a polybutylene layer useful for the production of bags |
Country Status (19)
Country | Link |
---|---|
US (1) | US4169910A (en) |
JP (1) | JPS555891A (en) |
AT (1) | ATA403479A (en) |
AU (1) | AU528974B2 (en) |
BE (1) | BE876774A (en) |
CA (1) | CA1156812A (en) |
CH (1) | CH640179A5 (en) |
DE (1) | DE2921745A1 (en) |
DK (1) | DK231679A (en) |
FI (1) | FI69778C (en) |
FR (1) | FR2434034A1 (en) |
GB (1) | GB2025847B (en) |
IE (1) | IE48575B1 (en) |
IT (1) | IT1117797B (en) |
MX (1) | MX151018A (en) |
NL (1) | NL7904396A (en) |
NO (1) | NO791822L (en) |
NZ (1) | NZ190641A (en) |
SE (1) | SE7904789L (en) |
Cited By (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4229241A (en) * | 1978-12-04 | 1980-10-21 | W. R. Grace & Co. | Process for making a multi layer polyolefin shrink film |
US4230767A (en) * | 1978-02-08 | 1980-10-28 | Toyo Boseki Kabushiki Kaisha | Heat sealable laminated propylene polymer packaging material |
WO1982000441A1 (en) * | 1980-08-08 | 1982-02-18 | Travenol Lab Baxter | Clear,autoclavable,sealed container having good water vapor barrier properties and flex crack resistance |
US4316970A (en) * | 1980-08-01 | 1982-02-23 | Shell Oil Company | Blends of butene-1-ethylene copolymer and polypropylene |
US4354004A (en) * | 1981-09-28 | 1982-10-12 | Shell Oil Company | Film compositions from olefin polymer blends |
US4364981A (en) * | 1979-12-28 | 1982-12-21 | Union Carbide Corporation | Three layer film having a core layer of low pressure, low density polyethylene |
US4391862A (en) * | 1981-07-02 | 1983-07-05 | W. R. Grace & Co., Cryovac Division | Pasteurizable thermoplastic film and receptacle therefrom |
US4456660A (en) * | 1978-12-13 | 1984-06-26 | Mobil Oil Corporation | Coextruded two-ply laminate films of low density polyethylene and blend of polybutene-1 and polyethylene or polypropylene |
US4488924A (en) * | 1981-12-10 | 1984-12-18 | Mobil Oil Corporation | Method of sealing laminar thermoplastic films and bags |
US4528220A (en) * | 1984-02-09 | 1985-07-09 | Shell Oil Company | Plastic bags for medical solutions and blood |
US4677007A (en) * | 1984-11-30 | 1987-06-30 | C-I-L, Inc. | Thermoplastic sack |
US4778697A (en) * | 1985-11-29 | 1988-10-18 | American National Can Company | Polymeric films |
US4965108A (en) * | 1985-09-11 | 1990-10-23 | First Brands Corporation | Low temperature impact and puncture resistant thermoplastic films and bags therefrom |
US4965109A (en) * | 1987-03-09 | 1990-10-23 | First Brands Corporation | Low temperature impact and puncture resistant polypropyene films layered films and bags therefrom |
US4966795A (en) * | 1985-11-29 | 1990-10-30 | American National Can Company | Multiple layer sheet structures and package |
US5011719A (en) * | 1985-11-29 | 1991-04-30 | American National Can Company | Polymeric compositions and films |
US5035851A (en) * | 1986-11-25 | 1991-07-30 | W. R. Grace & Co.-Conn. | Method of making very high barrier film |
US5093164A (en) * | 1985-11-29 | 1992-03-03 | Bauer Frank T | Multiple layer packaging sheet material |
US5433908A (en) * | 1991-03-20 | 1995-07-18 | Kuraray Co., Ltd. | Method for the production of a multi-layer construction film |
US6017832A (en) * | 1996-09-04 | 2000-01-25 | Kimberly-Clark Worldwide, Inc. | Method and composition for treating substrates for wettability |
US6072005A (en) * | 1997-10-31 | 2000-06-06 | Kimberly-Clark Worldwide, Inc. | Breathable films and process for producing them |
US6204208B1 (en) | 1996-09-04 | 2001-03-20 | Kimberly-Clark Worldwide, Inc. | Method and composition for treating substrates for wettability and skin wellness |
US6296936B1 (en) | 1996-09-04 | 2001-10-02 | Kimberly-Clark Worldwide, Inc. | Coform material having improved fluid handling and method for producing |
US6869666B2 (en) | 2001-05-02 | 2005-03-22 | 3M Innovative Properties Company | Controlled-puncture films |
US20060285783A1 (en) * | 2006-06-01 | 2006-12-21 | Burnett John A Jr | Fluorescent buld disposal bag |
US7316833B1 (en) | 1993-06-24 | 2008-01-08 | Penchiney Emballage Flexible Europe | Multi-layer thermoplastic films and packages made therefrom |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58160147A (en) * | 1982-03-18 | 1983-09-22 | 三井化学株式会社 | Coextruded multilayer film |
US6524720B1 (en) | 1992-09-18 | 2003-02-25 | Cryovac, Inc. | Moisture barrier film |
CA2106258C (en) * | 1992-09-18 | 2003-11-04 | Gautam P. Shah | Moisture barrier film |
DE19806475A1 (en) * | 1998-02-17 | 1999-08-19 | Wolff Walsrode Ag | Multi-layer sealing layer and hermetically sealable packaging material made with it |
JP6315798B2 (en) * | 2014-06-27 | 2018-04-25 | サン・トックス株式会社 | Multilayer sealant film |
JPWO2021192536A1 (en) | 2020-03-26 | 2021-09-30 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3524795A (en) * | 1965-07-01 | 1970-08-18 | Dow Chemical Co | Packaging film |
US3997383A (en) * | 1975-03-10 | 1976-12-14 | W. R. Grace & Co. | Cross-linked amide/olefin polymeric laminates |
US4046945A (en) * | 1974-01-18 | 1977-09-06 | Chemische Werke Huls Aktiengesellschaft | Process for the bonding of films and molded components |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE561516A (en) * | 1956-10-11 | |||
US3891008A (en) * | 1973-12-26 | 1975-06-24 | Grace W R & Co | Multi-layer thermoplastic film and method of making same |
GB1497577A (en) * | 1975-06-11 | 1978-01-12 | Ici Ltd | Film-forming olefin polymer compositions |
-
1978
- 1978-06-28 US US05/919,852 patent/US4169910A/en not_active Expired - Lifetime
-
1979
- 1979-05-29 DE DE19792921745 patent/DE2921745A1/en not_active Withdrawn
- 1979-05-29 CA CA000328571A patent/CA1156812A/en not_active Expired
- 1979-05-31 NO NO791822A patent/NO791822L/en unknown
- 1979-05-31 SE SE7904789A patent/SE7904789L/en not_active Application Discontinuation
- 1979-06-01 DK DK231679A patent/DK231679A/en not_active Application Discontinuation
- 1979-06-04 IT IT4929479A patent/IT1117797B/en active
- 1979-06-05 BE BE0/195573A patent/BE876774A/en not_active IP Right Cessation
- 1979-06-05 NL NL7904396A patent/NL7904396A/en not_active Application Discontinuation
- 1979-06-05 CH CH523579A patent/CH640179A5/en not_active IP Right Cessation
- 1979-06-05 JP JP7050779A patent/JPS555891A/en active Pending
- 1979-06-05 AT AT403479A patent/ATA403479A/en not_active IP Right Cessation
- 1979-06-05 FR FR7914292A patent/FR2434034A1/en active Granted
- 1979-06-05 NZ NZ19064179A patent/NZ190641A/en unknown
- 1979-06-05 FI FI791794A patent/FI69778C/en not_active IP Right Cessation
- 1979-06-05 MX MX177941A patent/MX151018A/en unknown
- 1979-06-05 GB GB7919525A patent/GB2025847B/en not_active Expired
- 1979-06-07 AU AU47858/79A patent/AU528974B2/en not_active Ceased
- 1979-08-08 IE IE1102/79A patent/IE48575B1/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3524795A (en) * | 1965-07-01 | 1970-08-18 | Dow Chemical Co | Packaging film |
US4046945A (en) * | 1974-01-18 | 1977-09-06 | Chemische Werke Huls Aktiengesellschaft | Process for the bonding of films and molded components |
US3997383A (en) * | 1975-03-10 | 1976-12-14 | W. R. Grace & Co. | Cross-linked amide/olefin polymeric laminates |
Cited By (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4230767A (en) * | 1978-02-08 | 1980-10-28 | Toyo Boseki Kabushiki Kaisha | Heat sealable laminated propylene polymer packaging material |
US4229241A (en) * | 1978-12-04 | 1980-10-21 | W. R. Grace & Co. | Process for making a multi layer polyolefin shrink film |
US4456660A (en) * | 1978-12-13 | 1984-06-26 | Mobil Oil Corporation | Coextruded two-ply laminate films of low density polyethylene and blend of polybutene-1 and polyethylene or polypropylene |
US4364981A (en) * | 1979-12-28 | 1982-12-21 | Union Carbide Corporation | Three layer film having a core layer of low pressure, low density polyethylene |
US4316970A (en) * | 1980-08-01 | 1982-02-23 | Shell Oil Company | Blends of butene-1-ethylene copolymer and polypropylene |
US4322465A (en) * | 1980-08-08 | 1982-03-30 | Baxter Travenol Laboratories, Inc. | Clear, autoclavable, sealed container having good water vapor barrier properties and flex crack resistance |
WO1982000441A1 (en) * | 1980-08-08 | 1982-02-18 | Travenol Lab Baxter | Clear,autoclavable,sealed container having good water vapor barrier properties and flex crack resistance |
US4391862A (en) * | 1981-07-02 | 1983-07-05 | W. R. Grace & Co., Cryovac Division | Pasteurizable thermoplastic film and receptacle therefrom |
US4354004A (en) * | 1981-09-28 | 1982-10-12 | Shell Oil Company | Film compositions from olefin polymer blends |
US4488924A (en) * | 1981-12-10 | 1984-12-18 | Mobil Oil Corporation | Method of sealing laminar thermoplastic films and bags |
US4528220A (en) * | 1984-02-09 | 1985-07-09 | Shell Oil Company | Plastic bags for medical solutions and blood |
US4677007A (en) * | 1984-11-30 | 1987-06-30 | C-I-L, Inc. | Thermoplastic sack |
US4965108A (en) * | 1985-09-11 | 1990-10-23 | First Brands Corporation | Low temperature impact and puncture resistant thermoplastic films and bags therefrom |
US4778697A (en) * | 1985-11-29 | 1988-10-18 | American National Can Company | Polymeric films |
US4966795A (en) * | 1985-11-29 | 1990-10-30 | American National Can Company | Multiple layer sheet structures and package |
US5011719A (en) * | 1985-11-29 | 1991-04-30 | American National Can Company | Polymeric compositions and films |
US5093164A (en) * | 1985-11-29 | 1992-03-03 | Bauer Frank T | Multiple layer packaging sheet material |
US5035851A (en) * | 1986-11-25 | 1991-07-30 | W. R. Grace & Co.-Conn. | Method of making very high barrier film |
US4965109A (en) * | 1987-03-09 | 1990-10-23 | First Brands Corporation | Low temperature impact and puncture resistant polypropyene films layered films and bags therefrom |
US5433908A (en) * | 1991-03-20 | 1995-07-18 | Kuraray Co., Ltd. | Method for the production of a multi-layer construction film |
US7316833B1 (en) | 1993-06-24 | 2008-01-08 | Penchiney Emballage Flexible Europe | Multi-layer thermoplastic films and packages made therefrom |
US6017832A (en) * | 1996-09-04 | 2000-01-25 | Kimberly-Clark Worldwide, Inc. | Method and composition for treating substrates for wettability |
US6204208B1 (en) | 1996-09-04 | 2001-03-20 | Kimberly-Clark Worldwide, Inc. | Method and composition for treating substrates for wettability and skin wellness |
US6296936B1 (en) | 1996-09-04 | 2001-10-02 | Kimberly-Clark Worldwide, Inc. | Coform material having improved fluid handling and method for producing |
US6072005A (en) * | 1997-10-31 | 2000-06-06 | Kimberly-Clark Worldwide, Inc. | Breathable films and process for producing them |
US6869666B2 (en) | 2001-05-02 | 2005-03-22 | 3M Innovative Properties Company | Controlled-puncture films |
US20060285783A1 (en) * | 2006-06-01 | 2006-12-21 | Burnett John A Jr | Fluorescent buld disposal bag |
Also Published As
Publication number | Publication date |
---|---|
DK231679A (en) | 1979-12-29 |
SE7904789L (en) | 1979-12-29 |
FR2434034B1 (en) | 1984-04-06 |
CH640179A5 (en) | 1983-12-30 |
IE791102L (en) | 1979-12-28 |
GB2025847B (en) | 1983-03-30 |
MX151018A (en) | 1984-09-07 |
JPS555891A (en) | 1980-01-17 |
NL7904396A (en) | 1980-01-03 |
DE2921745A1 (en) | 1980-01-03 |
BE876774A (en) | 1979-12-05 |
IE48575B1 (en) | 1985-03-06 |
IT7949294A0 (en) | 1979-06-04 |
FI791794A (en) | 1979-12-29 |
ATA403479A (en) | 1986-02-15 |
GB2025847A (en) | 1980-01-30 |
FI69778B (en) | 1985-12-31 |
NZ190641A (en) | 1981-03-16 |
AU528974B2 (en) | 1983-05-19 |
FI69778C (en) | 1986-05-26 |
NO791822L (en) | 1980-01-02 |
AU4785879A (en) | 1980-01-03 |
FR2434034A1 (en) | 1980-03-21 |
IT1117797B (en) | 1986-02-24 |
CA1156812A (en) | 1983-11-15 |
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